US5561025A - Toner aggregation processes - Google Patents
Toner aggregation processes Download PDFInfo
- Publication number
- US5561025A US5561025A US08/497,996 US49799695A US5561025A US 5561025 A US5561025 A US 5561025A US 49799695 A US49799695 A US 49799695A US 5561025 A US5561025 A US 5561025A
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- United States
- Prior art keywords
- surfactant
- particles
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- percent
- water
- Prior art date
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- Expired - Lifetime
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- 238000004220 aggregation Methods 0.000 title claims description 31
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- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 claims abstract description 24
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- 239000003999 initiator Substances 0.000 claims abstract description 15
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 239000010419 fine particle Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- WNWZKKBGFYKSGA-UHFFFAOYSA-N n-(4-chloro-2,5-dimethoxyphenyl)-2-[[2,5-dimethoxy-4-(phenylsulfamoyl)phenyl]diazenyl]-3-oxobutanamide Chemical compound C1=C(Cl)C(OC)=CC(NC(=O)C(N=NC=2C(=CC(=C(OC)C=2)S(=O)(=O)NC=2C=CC=CC=2)OC)C(C)=O)=C1OC WNWZKKBGFYKSGA-UHFFFAOYSA-N 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical class OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical class Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
Definitions
- the present invention is generally directed to toner processes, and more specifically, to the preparation of resin particles by emulsion polymerization, and which resin particles can be selected for use in toner aggregation and coalescence processes, reference, for example, U.S. Pat. Nos. 5,344,738; 5,403,693; 5,418,108; and 5,364,729, the disclosures of which are totally incorporated herein by reference.
- the present invention is directed to the economical in situ chemical preparation of toners without the utilization of the known pulverization and/or classification methods, and wherein toners with an average volume diameter of from about 1 to about 25, and preferably from 1 to about 10 microns, and narrow size distribution can be obtained, the size distribution as measured by GSD being in the range, for example, of about 1.05 to about 1.40, and preferably in the range of 1.05 to 1.3.
- the resulting toners can be selected for known electrophotographic imaging and printing processes, including color processes, and lithography.
- the present invention is directed to emulsion polymerization processes whereby the colloidal properties of the resulting resin particles can be controlled in a manner that the latexes of resin particles may be aggregated and coalesced in the processes described in U.S. Pat. No. 5,403,693, and in similar processes, over a wider range of conditions and, therefore, with improved consistency and reproducibility.
- U.S. Pat. No. 5,403,693 illustrates the addition of extra stabilizer after the formation and before the coalescence, or fusing of the desired aggregates, thereby "freezing" the aggregate size prior to the coalescence step.
- the aggregates may exhibit an increased tendency to grow further in size during the coalescence step and the GSD of the particle size distribution will tend to increase, whereas if too much extra stabilizer is added, then the aggregates may begin to break apart. Since both the further growth/increase in GSD and the breaking apart of aggregates are generally not desired, there exists a need for a process wherein a limited range of concentrations of extra stabilizer can be used to "freeze" the aggregates without producing either undesirable growth or breakage. For aggregates formed from some latexes, this range is quite narrow, or may even not exist, because the latex properties are not optimized for the aggregation process.
- the present invention is directed, in embodiments, to the use during emulsion polymerization of reagents that ensure adequate termination, for example by chain transfer termination, of growing oligomer chains either in the water phase or at the interfaces between the water and particle phases, phases which coexist during emulsion polymerization, to produce latex particles with colloidal properties that are more desirable for aggregation-coalescence processes than the properties of similar latexes made without such reagents.
- the particle phase refers to the growing particles, which comprise resin polymer, such as poly(styrene-co-butyl acrylate); monomer, such as styrene and butyl acrylate; and other reagents, or components, such as termination transfer agents, surfactants, and polar comonomers.
- resin polymer such as poly(styrene-co-butyl acrylate); monomer, such as styrene and butyl acrylate
- other reagents, or components such as termination transfer agents, surfactants, and polar comonomers.
- termination agents such as alkyl thiols, can be selected, such as from about 0.0002 moles per 100 grams of monomer to about 0.09 moles per 100 grams of monomer, and preferably from about 0.0005 moles per 100 grams of monomer to about 0.04 moles per 100 grams of monomer.
- the present invention in embodiments utilizes the above mentioned class of termination agents in the emulsion polymerization step to minimize or eliminate the breakdown of aggregated particles that may occur when practicing the processes disclosed in U.S. Pat. No. 5,403,693 and similar processes, thereby resulting in a superior process wherein the particle size is controlled over a substantially wider range of conditions.
- particles with a large number of charge groups of the same sign chemically bound to their surface will not experience as large an attraction to one another, since the charge groups on two neighboring particles will repel one another. These repulsions between the charge groups can render it more difficult for the particles to come into close contact. Even the hydrophilicity of polar but uncharged groups chemically bound to the surface may render it more difficult for the particles to come into close contact.
- the polar comonomers may react to form polar groups which are chemically bound to the surfaces of particles, depending on the process and whether the disclosed termination agents are absent, which can prevent a sufficiently strong attraction from forming between two aggregating particles. When the attraction is not sufficiently strong, the aggregates formed from such particles will have a greater tendency to break apart.
- polar comonomers with groups that can dissociate to yield charged groups (e.g. acidic or basic comonomers such as acrylic acid)
- the polar comonomers may react to form polar groups which are chemically bound to the surfaces of particles, depending on the process and whether the disclosed termination agents are absent, which can prevent a sufficiently strong attraction from forming between two aggregating particles. When the attraction is not sufficiently strong, the aggregates formed from such particles will have a greater tendency to break apart.
- Agents which ensure adequate termination of growing chains either in the water phase or at the interfaces between the water and particle phases can be used in the emulsion polymerization to minimize or eliminate this problem, since such agents can reduce the number of such polar groups that are chemically bound to the surfaces of the resin particles.
- such agents are, therefore, added in large enough amounts to ensure the desired termination, and the processing conditions are also chosen to ensure the desired termination, yielding latex particles with the desired colloidal properties.
- polar comonomers can react to become a part of either (i) species that reside primarily in the water phase, (ii) interfacially active species that adsorb onto the resin particles, or (iii) polymer chains that are incorporated into the bulk of the emulsion particles.
- the polar comonomer units are chemically bound to the particle and will have very limited mobility below the glass transition temperature of the polymer, once the polymerization is completed; furthermore, such units will reside either at the surface or in the interior of the particles.
- Polar comonomer units which are chemically bound to the surface of the emulsion particles may weaken the aggregation of particles, and the use of termination agents reduces the degree to which such comonomers become chemically bound to the surfaces of the emulsion particles, thereby reducing or eliminating the problems arising from a weakened aggregation.
- polar groups When polar groups are chemically bound to the surfaces of latex particles, they may form a permanent barrier between aggregated latex particles which keeps the latex particles from strong attraction to each other.
- adsorbed, but not chemically bound, interfacially active species containing polar units can change positions along the surface, as well as desorb, in order to allow the formation of closer and stronger attractions between primary particles.
- initiation of growing chains occurs primarily in the water phase, and the growing chains add polar comonomer units in relation to their concentration in the water phase.
- these growing chains eventually enter and incorporate into a particle, which may not be optimal for aggregation processes, however, the incorporation can be reduced by ensuring that a sufficient number of the growing chains are terminated either in the water phase or at the interface between the water and particle phases.
- the resulting molecules will then fall under (i) or (ii), rather than (iii), thus yielding latex particles with more favorable colloidal properties.
- Termination agents such as certain chain transfer agents, with sufficient reactivity in the water phase or at the interfaces between the water and particle phases, can be used to effect the desired termination in polymerization processes.
- the present invention is directed to processes for controlling the colloidal properties of resin particles through the use of termination agents, including certain types of chain transfer agents, that ensure the mode of termination described herein, and in polymerizations with polar comonomers.
- termination agents including certain types of chain transfer agents, that ensure the mode of termination described herein, and in polymerizations with polar comonomers.
- some chain transfer agents used to modify the molecular weight of the resin are also effective in causing the mode of termination described above, but other chain transfer agents used to modify the molecular weight of the resin are not effective in this role.
- the present invention is directed to synthesizing a latex for use in aggregation/coalescence processes for preparing toner, e.g. processes disclosed in U.S. Pat. No. 5,403,693, wherein a stabilizer is added to a suspension of aggregates prior to heating the aggregates to a sufficiently high temperature to enable fusing, or coalescence, of the aggregates, the action of the stabilizer being the prevention of further growth of the aggregates during the coalescence stage.
- termination agents during preparation of latexes by emulsion polymerization, namely, agents such as certain chain transfer agents which are believed to cause adequate termination either in the aqueous phase or at the interfaces of reacting latex particles during emulsion polymerization with polar comonomers, results in latex particles with improved colloidal properties in that breakup of aggregates during the coalescence stage is minimized or prevented with better control and over a wider range of conditions than is often achieved otherwise.
- the present invention is directed, in embodiments, to an in situ process comprised of (i) first dispersing a pigment, such as SUNSPERSE CYANTM or SUNSPERSE REDTM, in an aqueous mixture containing a cationic surfactant, such as benzalkonium chloride (SANIZOL B-50TM), utilizing a high shearing device, such as an IKA/Brinkmann Polytron, or microfluidizer or sonicator; (ii) thereafter shearing this mixture with a charged latex of suspended resin particles, such as poly(styrene/butylacrylate/acrylic acid), synthesized using a termination agent which ensures adequate termination either in the aqueous phase or at the interfaces of emulsion particles, of particle size ranging from about 0.01 to about 0.5 micron as measured by the Brookhaven nanosizer, in an aqueous surfactant mixture containing an anionic surfactant, such as sodium dodecylbenzene s
- statically bound aggregates ranging in size of from about 0.5 micron to about 10 microns in volume average diameter size as measured by the Coulter Counter (Microsizer II); and (iv) adding concentrated (from about 5 percent to about 30 percent) aqueous surfactant solution containing an anionic surfactant, such as sodium dodecylbenzene sulfonate, for example NEOGEN RTM or NEOGEN SCTM, or nonionic surfactant, such as alkyl phenoxy poly(ethyleneoxy) ethanol, for example IGEPAL 897TM or ANTAROX 897TM, in controlled amounts to prevent any changes in particle size and in GSD of the size distribution, which can range from about 1.16 to about 1.28, during the heating step, and thereafter, heating to 10° to 50° C.
- an anionic surfactant such as sodium dodecylbenzene sulfonate, for example NEOGEN RTM or NEOGEN SCTM
- nonionic surfactant such as alkyl phenoxy poly
- toner particles comprised of resin and pigment with various particle size diameters can be obtained, such as from 1 to 12 microns in average volume particle diameter, and preferably in the range of 3 to 9 microns, and wherein the stirring speed in (iii) is reduced in (iv) as illustrated in U.S. Pat. No. 5,403,693.
- the aforementioned toners are especially useful for the development of colored images with excellent line and solid resolution, and wherein substantially no background deposits are present.
- This invention is directed in embodiments to the synthesis of latex particles whereby the behavior of the suspended aggregates in the heating, or coalescence step is improved by the use during the emulsion polymerization of termination agents, such as chain transfer agents, which can increase the rate of termination of growing chains in the water phase or at the interfaces between the particles and the water phase.
- termination agents such as chain transfer agents
- a termination agent for example 1-butanethiol, 1-octanethiol or CBr 4
- a termination agent for example 1-butanethiol, 1-octanethiol or CBr 4
- a chain transfer agent with sufficient water solubility or interfacial activity, during formation or growth by emulsion polymerization of resin particles
- anionic or nonionic surfactant added to already formed aggregates, as disclosed in U.S. Pat. No.
- the aggregates may break apart into smaller entities upon addition of this extra stabilizer and subsequent heating, which is detrimental to the process and product.
- the tendency of the aggregates to break apart, when it occurs, may be reduced or eliminated by using a sufficient amount of any terminating agent capable of causing adequate termination of growing chains either in the water phase or at the interface between the water and particle phases when preparing the latex by, for example, emulsion polymerization.
- U.S. Patent 4,996, 127 a toner of associated particles of secondary particles comprising primary particles of a polymer having acidic or basic polar groups and a coloring agent.
- the polymers selected for the toners of this '127 patent can be prepared by an emulsion polymerization method, see for example columns 4 and 5 of this patent.
- column 7 of this '127 patent it is indicated that the toner can be prepared by mixing the required amount of coloring agent and optional charge additive with an emulsion of the polymer having an acidic or basic polar group obtained by emulsion polymerization.
- statically bound aggregated particles to form said toner composition comprised of polymeric resin, pigment and optionally a charge control agent.
- the present patent application teaches the use of termination agents in the preparation of polymer particles by emulsion polymerization in a manner that reduces the tendency of the aggregates formed from such particles to break apart in, for example, the emulsion/aggregation process described in U.S. Pat. No. 5,403,693.
- the processes for favorably modifying the colloidal properties of the latex comprise performing emulsion polymerization with reagents that ensure adequate termination, for example by chain transfer termination, of growing oligomer chains either in the water phase or at the interfaces between the water and particle phases, phases which coexist during emulsion polymerizations.
- These agents should be added in large enough amounts to ensure the desired termination.
- adequate amounts of alkyl thiol termination agents generally employed in embodiments are from about 0.0002 moles per 100 grams of monomer to about 0.09 moles per 100 grams of monomer, and preferably from about 0.0005 moles per 100 grams of monomer to about 0.04 moles per 100 grams of monomer.
- toner with an average particle diameter of from between about 1 to about 50 microns, and preferably from about 1 to about 7 microns, and with a narrow GSD of from about 1.2 to about 1.3 and preferably from about 1.16 to about 1.25 as measured by the Coulter Counter.
- composite polar or nonpolar toner compositions in high yields of from about 90 percent to about 100 percent by weight of toner without resorting to classification.
- toner compositions with low fusing temperatures of from about 110° C. to about 150° C., and with excellent blocking characteristics at from about 50° C. to about 60° C.
- toner compositions with a high projection efficiency such as from about 75 to about 95 percent efficiency as measured by the Match Scan II spectrophotometer available from Milton-Roy.
- toners and processes thereof there are provided processes for the economical direct chemical preparation of toner compositions by an improved flocculation or coagulation, and coalescence processes, and wherein the latex is synthesized in part or in entirety by an improved emulsion polymerization with polar comonomers and a termination agent that can increase the termination in the water phase or at the interface between the latex particles and the water, the termination being of oligomers containing the polar comonomer, thereby yielding latex particles with desirable colloidal properties, as evidenced by superior behavior with respect to aggregate stability during aggregation.
- the present invention is directed to a process for the preparation of polymer latex particles which comprises the emulsion polymerization of a mixture of monomer, polar comonomer, water, surfactant, initiator, and a water phase termination agent, and wherein the water phase termination agent is selected from the group consisting of butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, and carbon tetrabromide (CBr 4 ).
- the resin selected for the process of the present invention can be prepared by utilizing emulsion polymerization techniques or by utilizing other heterogeneous polymerization processes, such as polymer microsuspension processes or polymer solution microsuspension processes, in which more than one phase coexists and termination of growing chains in the continuous phase can alter the colloidal properties of the resulting discrete resin particles.
- the monomers utilized in such processes can be, for example, styrene, acrylates, methacrylates, butadiene, isoprene, and the like together with polar comonomers, such as acidic or basic olefinic monomers like acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternary ammonium halide of dialkyl or trialkyl acrylamides or methacrylamide, vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, and the like.
- Known chain transfer agents such as 1-dodecanethiol, can also be selected to modify the molecular weight when preparing resin particles.
- Either surfactant or surfactant free emulsion polymerizations can be used to produce the latex particles, and if surfactants are added, they can be anionic, nonionic, cationic surfactants, or a mixture thereof.
- Initiators utilized in such processes can be, for example, ammonium persulfate, potassium persulfate, and other initiator substances with sufficient solubility in water.
- a termination agent or combination of termination agents, which can ensure adequate termination in the water phase or at the interfaces of growing particles and the water phase, is (are) to be used as an essential reactant (as essential reactants) in the polymerization processes disclosed by this invention.
- the reaction can be performed using known polymerization protocols, including batch and semi-batch emulsion polymerization.
- the latex is aggregated and coalesced according to U.S. Pat. No. 5,403,693 or another aggregation-coalescence process.
- Other processes for obtaining resin particles of from about 0.01 micron to about 3 microns can be selected from polymer microsuspension process, such as disclosed in U.S. Pat. No. 3,674,736, the disclosure of which is totally incorporated herein by reference, and polymer solution microsuspension process, such as disclosed in U.S. Pat. No. 5,290,654, the disclosure of which is totally incorporated herein by reference.
- Illustrative examples of resin particles produced with the processes of the present invention include particles of known polymers such as poly(styrene-butadiene), poly(para-methyl styrene-butadiene), poly(meta-methyl styrene-butadiene), poly(alpha-methyl styrene-butadiene), poly(methylmethacrylate-butadiene), poly(ethylmethacrylate-butadiene), poly(propylmethacrylate-butadiene), poly(butylmethacrylate-butadiene), poly(methylacrylate-butadiene), poly(ethylacrylate-butadiene), poly(propylacrylate-butadiene), poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(para-methyl styrene-isoprene), poly(meta-methyl styrene-isoprene), poly(al
- the resin selected for the process of the present invention generally can be in embodiments styrene acrylates, styrene butadienes, styrene methacrylates, or the like, and are present in various effective amounts, such as from about 85 weight percent to about 98 weight percent of the toner, and can be of small average particle size, such as from about 0.01 micron to about 1 micron in average volume diameter as measured by the Brookhaven nanosize particle analyzer.
- termination agents to ensure adequate termination in the water phase or at the interfaces of particles and the water phase can be, for example, chain transfer agents with sufficient reactivity in the water or at interfaces, such as carbon tetrabromide, 1-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, and 1-octanethiol, and isomers of these compounds; monomers that exhibit sufficiently high termination that their use ensures the desired termination in the water phase; and retarders, of which allyl acetate is an example.
- chain transfer agents with sufficient reactivity in the water or at interfaces, such as carbon tetrabromide, 1-butanethiol, 1-pentanethiol, 1-hexanethiol, 1-heptanethiol, and 1-octanethiol, and isomers of these compounds; monomers that exhibit sufficiently high termination that their use ensures the desired termination in the water phase; and retarders, of which
- alkyl mercaptans all are known chain transfer agents and can affect the molecular weight of species during polymerizations, however, 1-dodecanethiol has negligible solubility in water, and thus does not effectively act as an agent for termination either in the water phase or at the interfaces between the particle and water phases. Conversely, the lower homologs can yield latex particles with the desired properties, when present in sufficient concentrations, as demonstrated in the Examples below.
- the effective concentrations of the disclosed class of termination agents are set primarily by the ability to ensure adequate termination as described herein, and the concentration will vary from species to species depending on the termination kinetics and the solubility of the termination agent in the continuous phase of the polymerization, for example water; given this clarification, an effective concentration of alkyl thiols generally employed in embodiments to ensure adequate termination in the aqueous phase or at the interfaces between the particle and aqueous phases is, as an example, from about 0.0002 moles per 100 grams of monomer to about 0.09 moles per 100 grams of monomer, and preferably from about 0.0005 moles per 100 grams of monomer to about 0.04 moles per 100 grams of monomer.
- the present invention is directed to in situ processes for the preparation of toner compositions which comprises (i) preparing an ionic pigment mixture by dispersing a pigment, such as carbon black like REGAL 330®, HOSTAPERM PINKTM, or PV FAST BLUETM, of from about 2 to about 10 percent by weight of toner in an aqueous mixture cationic surfactant, such as dialkylbenzene dialkylammonium chloride like SANIZOL B-50TM available from Kao or MIRAPOLTM available from Alkaril Chemicals, of from about 0.5 to about 2 percent by weight of water, utilizing a high shearing device, such as a Brinkmann Polytron or IKA homogenizer at a speed of from about 3,000 revolutions per minute to about 10,000 revolutions per minute for a duration of from about 1 minute to about 120 minutes; (ii) adding the aforementioned ionic pigment mixture to an aqueous suspension of containing resin particles comprised of, for example, poly(styrene), or PV
- the resin Tg is preferably 54° C., for 1 to 24 hours to form electrostatically stable aggregates of from about 0.5 micron to about 5 microns in average volume diameter; (iv) adding extra anionic surfactant or nonionic surfactant in the amount of from 0.5 percent to 5 percent by weight of the water to stabilize aggregates formed in the previous step; (v) heating the statically bound aggregate composite particles at from about 60° C. to about 95° C., for example from about 5° C. to about 50° C.
- additives to improve flow characteristics, and charge additives to improve charging characteristics may then optionally be added by blending with the toner, such additives including AEROSILS® or silicas, metal oxides like tin, titanium and the like of from about 0.1 to about 10 percent by weight of the toner.
- Various known colorants or pigments present in the toner in an effective amount of, for example, from about 1 to about 25 percent by weight of the toner, and preferably in an amount of from about 1 to about 15 weight percent that can be selected include carbon black like REGAL 330®, REGAL 330R®, REGAL 660®, REGAL 660R®, REGAL 400®, REGAL 400R®, and other equivalent black pigments.
- As colored pigments there can be selected known cyan, magenta, blue, red, green, brown, yellow, or mixtures thereof.
- pigments include phthalocyanine HELIOGEN BLUE L6900TM, D6840TM, D7080TM, D7020TM, PYLAM OIL BLUETM, PYLAM OIL YELLOWTM, PIGMENT BLUE 1TM available from Paul Uhlich & Company, Inc., PIGMENT VIOLET 1TM, PIGMENT RED 48TM, LEMON CHROME YELLOW DCC 1026TM, E.D. TOLUIDINE REDTM and BON RED CTM available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAperm YELLOW FGLTM, HOSTAPERM PINK ETM from Hoechst, and CINQUASIA MAGENTATM available from E.I.
- colored pigments that can be selected are cyan, magenta, or yellow pigments.
- magenta materials that may be selected as pigments include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as CI 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as CI 26050, CI Solvent Red 19, and the like.
- the color Index
- the toner may also include known charge additives in effective amounts of, for example, from 0.1 to 5 weight percent such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which illustrates a toner with a distearyl dimethyl ammonium methyl sulfate charge additive, the disclosures of which are totally incorporated herein by reference, negative charge additives like aluminum complexes, and the like.
- charge additives in effective amounts of, for example, from 0.1 to 5 weight percent such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which illustrates a toner with a distearyl dimethyl ammonium methyl
- Surfactants in amounts of, for example, 0.1 to about 25 weight percent in embodiments include, for example, nonionic surfactants such as dialkyphenoxypoly(ethyleneoxy) ethanol such as IGEPAL CA-210TM, IGEPAL CA-520TM, IGEPAL CA-720TM, IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, IGEPAL CA-210TM, ANTAROX 890TM, ANTAROX 897TM, and the like.
- An effective concentration of the nonionic surfactant is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.1 to about 5 percent by weight of monomers used to prepare the copolymer resin.
- ionic surfactants include anionic and cationic surfactants
- anionic surfactants include surfactants selected for the preparation of toners and the processes of the present invention are, for example, sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid available from Aldrich, NEOGEN RTM, NEOGEN SCTM available from Kao, and the like.
- An effective concentration of the anionic surfactant generally employed is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.1 to about 5 percent by weight.
- Examples of the cationic surfactants selected for the toners and processes of the present invention are, for example, dialkyl benzenealkyl ammonium chloride, lauryl trimethyl ammonium chloride, alkylbenzyl methyl ammonium chloride, alkyl benzyl dimethyl ammonium bromide, benzalkonium chloride, cetyl pyridinium bromide, C 12 , C 15 , C 17 trimethyl ammonium bromides, halide salts of quaternized polyoxyethylalkylamines, dodecylbenzyl triethyl ammonium chloride, MIRAPOLTM and ALKAQUATTM available from Alkaril Chemical Company, SANIZOLTM (benzalkonium chloride), available from Kao Chemicals, and the like, and mixtures thereof.
- dialkyl benzenealkyl ammonium chloride lauryl trimethyl ammonium chloride
- alkylbenzyl methyl ammonium chloride al
- This surfactant is utilized in various effective amounts, such as for example from about 0.1 percent to about 5 percent by weight of water.
- the molar ratio of the cationic surfactant used for flocculation to the anionic surfactant used in the latex preparation is in the range of about 0.5 to 4, and preferably from about 0.5 to 2.
- surfactant which are added to the aggregated particles to "freeze” or retain particle size and GSD achieved in the aggregation, can be selected from anionic surfactants, such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates available from Aldrich, NEOGEN RTM NEOGEN SCTM from Kao, and the like, reference U.S. Pat. No. 5,403,693.
- anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates available from Aldrich, NEOGEN RTM NEOGEN SCTM from Kao, and the like, reference U.S. Pat. No. 5,403,693.
- surfactants also include nonionic surfactants such as polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxy poly(ethyleneoxy) ethanol (available from Rhone-Poulenac as IGEPAL CA-210TM, IGEPAL CA-520TM, IGEPAL CA-720TM, IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, IGEPAL CA-210TM, ANTAROX 890TM and ANTAROX 897TM.
- An effective concentration of the anionic or nonionic surfactant generally employed in embodiments as a "freezing agent" or stabilizing agent is, for example, from about 0.01 to about 30 percent by weight, and preferably from about 0.5 to about 5 percent by weight of the total weight of the aggregated mixture.
- additives that can be added to the toner compositions after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silicas, mixtures thereof, and the like, which additives are usually present in an amount of from about 0.1 to about 2 weight percent, reference U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374 and 3,983,045, the disclosures of which are totally incorporated herein by reference.
- Preferred additives include zinc stearate and AEROSIL R972®, available from Degussa, in amounts of from 0.1 to 2 percent, which can be added, for example, during the aggregation process or blended into the formed toner product.
- Developer compositions can be prepared by mixing the toners obtained with the processes of the present invention with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference, for example from about 2 percent toner concentration to about 8 percent toner concentration.
- Latent images can then be developed with the aforementioned toner, reference for example U.S. Pat. No. 4,265,690, the disclosure of which is totally incorporated herein by reference.
- Pigment dispersion 9.6 grams of SUNSPERSETM BHD6000 cyan pigment dispersion were dispersed in 240 grams of water with 1.8 grams of SANIZOL B-50TM cationic surfactant alkylbenzyldimethyl ammonium chloride.
- a polymeric latex was prepared by emulsion polymerization of styrene/butylacrylate/acrylic acid, 82/18/2 parts (by weight) in nonionidanionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, 12 grams of 1-dodecanethiol, and 4 grams of carbon tetrabromide as the invention termination agent was mixed with 600 grams of deionized water in which 10 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM), and 4 grams of ammonium persulfate initiator were dissolved.
- NEOGEN RTM sodium dodecyl benzene sulfonate anionic surfactant
- Carbon tetrabromide is reported to have a solubility in water of about 7 ⁇ 10 -4 M at 30° C., and it exhibits a high chain transfer constant, thus it is expected to cause significant termination of oligomers in the aqueous phase at 80° C.
- the emulsion was then polymerized at 80° C.
- the aforementioned latex was then selected for the toner preparation of Example I.
- Coalescence of aggregated particles 70 milliliters of a solution of NEOGEN RTM sodium dodecylbenzenesulfonate anionic surfactant containing 20 percent of the anionic surfactant was added to the suspension of aggregates to prevent any further change in aggregate size.
- the stirring speed was reduced from 400 to 150 rpm, and the temperature of the aggregated particles in the kettle was then raised to 93° C., and kept at 93° C. for 4 hours to coalesce the aggregates.
- the resulting toner was comprised of about 95 percent of polymer, poly(styrene-butylacrylate-acrylic acid), and cyan pigment, about 5 percent by weight of toner, with an average volume diameter of 4.9 microns and a GSD of 1.19, indicating that by adding an extra amount of anionic surfactant prior to increasing the kettle temperature above the resin Tg to accomplish the coalescence, and reducing the stirring speed, one can retain particle size and GSD achieved in the aggregation step during coalescence, without the aggregates falling apart and without an excessive increase in particle size, when CBr 4 is added in the emulsion polymerization to ensure the formation of latex particles with desirable colloidal properties, presumedly by ensuring adequate termination of oligomers in the aqueous phase.
- the toner particles were then washed by filtration using hot water (50° C.) and dried on the freeze dryer.
- Pigment dispersion 12 grams of SUNSPERSETM BHD6000 cyan pigment dispersion was dispersed in 300 grams of water with 2.0 grams of SANIZOL B-50TM cationic surfactant alkylbenzyldimethyl ammonium chloride.
- a polymeric latex was prepared by emulsion polymerization of styrene/butylacrylate/acrylic acid, 82/18/2 parts (by weight), in nonionidanionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, and 12 grams of dodecanethiol were mixed with 600 grams of deionized water in which 10 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM which contains 60 percent of active component), 8.6 grams of polyoxyethylene nonyl phenyl ether--nonionic surfactant (ANTAROX 897TM--70 percent active), and 4 grams of ammonium persulfate initiator were dissolved.
- nonionidanionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, and 12 grams of dodecanethio
- Coalescence of aggregated particles 90 milliliters of a solution of NEOGEN RTM sodium dodecylbenzenesulfonate anionic surfactant containing 20 percent of the anionic surfactant were added to the suspension of aggregates to prevent any further change in aggregate size.
- the stirring speed was reduced from 400 to 150 rpm, and the temperature of the aggregated particles in the kettle was then raised to 93° C., and kept at 93° C. for 4 hours to coalesce the aggregates. After 5 minutes, the particle size was less than 1.35 microns, indicating that the aggregates were falling apart. All particle sizes were measured on a Coulter Counter Multisizer II.
- the aggregation at 45° C. was repeated with separate samples of the pigment dispersion and latex, after which the aggregates were coalesced without the addition of extra anionic surfactant.
- the stirring speed was reduced from 400 to 150 rpm, and the temperature of the aggregated particles in the kettle was then raised to 90° C., and kept at 90° C. for 4 hours to coalesce the aggregates; no anionic surfactant was added after the aggregation at 45° C. was completed.
- the aggregate size grew during the coalescence step to 10.1 microns with a GSD of 1.26.
- the particle size was 3.8 microns with a GSD of 1.19; after 3 hours, the particle size was 2.7 microns with a GSD of 1.34; and after 4 hours, the particle size was 1.5 microns with a GSD of 1.30, indicating that the aggregates were falling apart.
- Pigment dispersion 20 grams of SUNSPERSE MAGENTATM quinacridone pigment dispersion were dispersed in 240 grams of water with 2.3 grams of SANIZOL B-50TM cationic surfactant alkylbenzyldimethyl ammonium chloride.
- a polymeric latex was prepared by emulsion polymerization of styrene/butylacrylate/acrylic acid, 82/18/2 parts (by weight), in nonionic/anionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, 6 grams of 1-dodecanethiol, and 0.36 milliliter of 1-butanethiol as the invention terminating agent component were mixed with 600 grams of deionized water in which 10 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM which contains 60 percent of active 8.6 grams of polyoxyethylene nonyl phenyl ether--nonionic surfactant (ANTAROX 897TM--70 percent active), and 4 grams of ammonium persulfate initiator were dissolved.
- NEOGEN RTM sodium dodecyl benzene sulfonate anionic surfactant
- 1-Butanethiol is reported to have a solubility in water of about 7 ⁇ 10 -3 M at 25° C., and it exhibits a high chain transfer constant, so it is expected to cause significant termination of oligomers in the aqueous phase.
- the emulsion was then polymerized at 80° C. for 8 hours.
- the aforementioned latex was then selected for the toner preparation of Example II.
- Coalescence of aggregated particles 70 milliliters of a solution of NEOGEN RTM sodium dodecylbenzenesulfonate anionic surfactant containing 20 percent of the anionic surfactant were added to the suspension of aggregates to prevent any further change in aggregate size.
- the stirring speed was reduced from 400 to 150 rpm, and the temperature of the aggregated particles in the kettle was then raised to 93° C., and kept at 93° C. for 4 hours to coalesce the aggregates.
- the resulting toner was comprised of about 93 percent of polymer, poly(styrene-butylacrylate-acrylic acid), and magenta pigment, about 7 percent by weight of toner, with an average volume diameter of 3.5 microns and a GSD of 1.23, indicating that by adding an extra amount of anionic surfactant prior to increasing the kettle temperature above the resin Tg to accomplish the coalescence, and reducing the stirring speed, one can retain particle size and GSD achieved in the aggregation step during coalescence, without the aggregates falling apart, as evidenced by measurements with the above Coulter Counter, and without an excessive increase in particle size.
- the toner particles were then washed by filtration using hot water (50° C.) and dried on the freeze dryer.
- Pigment dispersion 7.6 grams of SUNSPERSETM BHD6000 cyan pigment dispersion were dispersed in 240 grams of water with 2.34 grams of SANIZOL B-50TM cationic surfactant alkylbenzyldimethyl ammonium chloride.
- a polymeric latex was prepared by emulsion polymerization of styrene/butylacrylate/acrylic acid, 82/18/2 parts (by weight), in nonionic/anionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, 6 grams of 1-dodecanethiol, and 1.8 milliliters of 1-butanethiol were mixed with 600 grams of deionized water in which 10 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM which contains 60 percent of active component), 8.6 grams of polyoxyethylene nonyl phenyl ether--nonionic surfactant (ANTAROX 897TM--70 percent active), and 4 grams of ammonium persulfate initiator were dissolved.
- nonionic/anionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8
- 1-Butanethiol is reported to have a solubility in water of about 7 ⁇ 10 -3 M at 25° C., and it exhibits a high chain transfer constant, so it is expected to cause significant termination of oligomers in the aqueous phase.
- the emulsion was then polymerized at 80° C. for 8 hours.
- the aforementioned latex was then selected for the toner preparation of Example III.
- Coalescence of aggregated particles 70 milliliters of a solution of NEOGEN RTM sodium dodecylbenzenesulfonate anionic surfactant containing 20 percent of the anionic surfactant were added to the suspension of aggregates to prevent any further change in aggregate size.
- the resulting toner was comprised of 96.2 percent of polymer, poly(styrene-butylacrylate-acrylic acid), and cyan pigment, about 3.8 percent by weight of toner, with an average volume diameter of 4.3 microns and a GSD of 1.18, indicating that by adding an extra amount of anionic surfactant prior to increasing the kettle temperature above the resin Tg to accomplish the coalescence, and reducing the stirring speed, one can retain particle size and GSD achieved in the aggregation step during coalescence, without the aggregates falling apart and without an excessive increase in particle size, when 1-butanethiol is added in the emulsion polymerization to ensure that latex particles with desirable colloidal properties are synthesized.
- the toner particles were then washed by filtration using hot water (50° C.) and dried on the freeze dryer.
- Pigment dispersion 7.6 grams of SUNSPERSETM BHD6000 cyan pigment dispersion were dispersed in 240 grams of water with 2.3 grams of SANIZOL B-50TM cationic surfactant alkylbenzyldimethyl ammonium chloride.
- a polymeric latex (sample E-69) was prepared by emulsion polymerization of styrene/butylacrylate/acrylic acid, 82/18/2 parts (by weight), in nonionic/anionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, and 16 grams of 1-dodecanethiol were mixed with 600 grams of deionized water in which 10 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM which contains 60 percent of active component), 8.6 grams of polyoxyethylene nonyl phenyl ether--nonionic surfactant (ANTAROX 897TM--70 percent active), and 4 grams of ammonium persulfate initiator were dissolved.
- nonionic/anionic surfactant solution as follows: 328 grams of styrene, 72 grams of butylacrylate, 8 grams of acrylic acid, and 16
- 1-Octanethiol has a solubility in water that is intermediate between 1-butanethiol and 1-dodecanethiol, so it is expected that the use of 1-octanethiol should more readily yield latex particles with superior aggregation-coalescence properties as described herein than 1-dodecanethiol. However, it is also expected that 1-octanethiol will not be as effective as 1-butanethiol and hence should be used at a larger concentration. Thus, the amount of 1-octanethiol in this Example is substantially larger than the amounts of 1-butanethiol in Examples II and III.
- 1-Butanethiol presents much more of an odor problem than 1-octanethiol, however, which may be more important in some applications than considerations about the amount of termination agent needed in a reaction.
- the emulsion was then polymerized at 80° C. for 8 hours.
- the resulting latex contained 60 percent of water and 40 percent of solids of the styrene-butyl acrylate-acrylic acid polymer, 82/18/2.
- the aforementioned latex was then selected for the toner preparation of Example IV.
- Coalescence of aggregated particles 80 milliliters of a solution of NEOGEN RTM sodium dodecylbenzenesulfonate anionic surfactant containing 20 percent of the anionic surfactant were added to the suspension of aggregates to prevent any further change in aggregate size.
- the resulting toner was comprised of 96 percent of polymer, poly(styrene-butylacrylate-acrylic acid), and cyan pigment, about 4 percent by weight of toner, with an average volume diameter of 5.9 microns and a GSD of 1.19, indicating that by adding an extra amount of anionic surfactant prior to increasing the kettle temperature above the resin Tg to accomplish the coalescence, and reducing the stirring speed, one can retain particle size and GSD achieved in the aggregation step during coalescence, without the aggregates falling apart and without an excessive increase in particle size, when 1-octanethiol is added in the emulsion polymerization to ensure that latex particles with desirable colloidal properties are synthesized.
- the toner particles were then washed by filtration using hot water (50° C.) and dried on the freeze dryer.
Abstract
Description
Claims (25)
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US08/497,996 US5561025A (en) | 1995-07-03 | 1995-07-03 | Toner aggregation processes |
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US08/497,996 US5561025A (en) | 1995-07-03 | 1995-07-03 | Toner aggregation processes |
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US5561025A true US5561025A (en) | 1996-10-01 |
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Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5766817A (en) * | 1997-10-29 | 1998-06-16 | Xerox Corporation | Toner miniemulsion process |
US5853943A (en) * | 1998-01-09 | 1998-12-29 | Xerox Corporation | Toner processes |
US5928829A (en) * | 1998-02-26 | 1999-07-27 | Xerox Corporation | Latex processes |
US5962178A (en) * | 1998-01-09 | 1999-10-05 | Xerox Corporation | Sediment free toner processes |
US5965316A (en) * | 1998-10-09 | 1999-10-12 | Xerox Corporation | Wax processes |
US6309787B1 (en) | 2000-04-26 | 2001-10-30 | Xerox Corporation | Aggregation processes |
US6346358B1 (en) | 2000-04-26 | 2002-02-12 | Xerox Corporation | Toner processes |
US6413692B1 (en) | 2001-07-06 | 2002-07-02 | Xerox Corporation | Toner processes |
US6455220B1 (en) | 2001-07-06 | 2002-09-24 | Xerox Corporation | Toner processes |
US6468727B2 (en) | 2000-02-05 | 2002-10-22 | Eastman Kodak Company | Nonionic oligomeric surfactants and their use as dispersants and stabilizers |
US6475691B1 (en) | 1997-10-29 | 2002-11-05 | Xerox Corporation | Toner processes |
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US5962178A (en) * | 1998-01-09 | 1999-10-05 | Xerox Corporation | Sediment free toner processes |
US5928829A (en) * | 1998-02-26 | 1999-07-27 | Xerox Corporation | Latex processes |
US5965316A (en) * | 1998-10-09 | 1999-10-12 | Xerox Corporation | Wax processes |
US6468727B2 (en) | 2000-02-05 | 2002-10-22 | Eastman Kodak Company | Nonionic oligomeric surfactants and their use as dispersants and stabilizers |
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US6346358B1 (en) | 2000-04-26 | 2002-02-12 | Xerox Corporation | Toner processes |
US6413692B1 (en) | 2001-07-06 | 2002-07-02 | Xerox Corporation | Toner processes |
US6455220B1 (en) | 2001-07-06 | 2002-09-24 | Xerox Corporation | Toner processes |
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